Process and apparatus for controlling reaction temperatures with heating arrangement in series flow

ABSTRACT

A process and apparatus for contacting reactants with a particulate catalyst while indirectly heating the reactants with a heat exchange medium improves temperature control by using an intermediate heat exchange fluid and system to prevent overheating of reactants and maintain parallel heating characteristics through multiple reaction-heat exchange zones. The internal flow path minimizes the circulation of the reaction zone heat exchange fluid by incorporating interstage reheating of the reaction zone heat exchange fluid as it passes in series flow. A particularly useful application of the process and apparatus is in the dehydrogenation of ethylbenzene to produce styrene. The process and apparatus can also be used with simultaneous exchange of catalyst particles by an operation that restricts reactant flow while moving catalyst through reaction stacks in which the reactant flow has been restricted.

CROSS-REFERENCE TO RELATED APPLICATION

This application is a Division of application Ser. No. 09/149,867 filedSep. 8, 1998, now U.S. Pat. No. 6,100,436, the contents of which arehereby incorporated by reference.

FIELD OF THE INVENTION

This invention relates to chemical reactors for the conversion of areaction fluid while indirectly heating a reaction with a heat exchangefluid.

BACKGROUND OF THE INVENTION

In many industries, like the petrochemical and chemical industries forinstance, the processes employ reactors in which chemical reactions areeffected in the components of one or more reaction fluids by contactwith a catalyst under given temperature and pressure conditions. Most ofthese reactions generate or absorb heat to various extents and are,therefore, exothermic or endothermic. The heating or chilling effectsassociated with exothermic or endothermic reactions can positively ornegatively affect the operation of the reaction zone. The negativeeffects can include among other things poor product production,deactivation of the catalyst, production of unwanted by-products, and inextreme cases, damage to the reaction vessel and associated piping. Moretypically, the undesired effects associated with temperature changeswill reduce the selectivity or yield of products from the reaction zone.

One solution to the problem has been the indirect heating of reactantsand/or catalysts within a reaction zone with a heating or coolingmedium. The most well known catalytic reactors of this type are tubulararrangements that have fixed or moving catalyst beds. The geometry oftubular reactors poses layout constraints that require large reactors orlimit throughput.

Indirect heat exchange has also been accomplished using thin plates todefine alternate channels that retain catalyst and reactants in one setof channels and a heat transfer fluid in alternate channels forindirectly heating or cooling the reactants and catalysts. Heat exchangeplates in these indirect heat exchange reactors can be flat or curvedand may have surface variations such as corrugations to increase heattransfer between the heat transfer fluids and the reactants andcatalysts. Although the thin heat transfer plates can, to some extent,compensate for the changes in temperature induced by the heat ofreaction, not all indirect heat transfer arrangements are able to offerthe complete temperature control that would benefit many processes bymaintaining a desired temperature profile through a reaction zone. Manyhydrocarbon conversion processes will operate more advantageously bymaintaining a temperature profile that differs from that created by theheat of reaction. In many reactions, the most beneficial temperatureprofile will be obtained by substantially isothermal conditions. In somecases, a temperature profile directionally opposite to the temperaturechanges associated with the heat of reaction will provide the mostbeneficial conditions. An example of such a case is in dehydrogenationreactions wherein the selectivity and conversion of the endothermicprocess is improved by having a rising temperature profile or reversetemperature gradient through the reaction zone. A specific arrangementfor heat transfer and reactant channels that offers more completecontrol can be found in U.S. Pat. No. 5,525,311, the contents of whichare hereby incorporated by reference.

Heating reactants within a reaction zone poses a number of limitationson the reactor arrangement and the operation of the process. A heatexchange reactor typically needs to operate with a large fluid mass flowrate of the heat transfer fluid in order to provide adequate mass fluxof the heat transfer fluid over the heat transfer surfaces. Failure tomaintain the adequate heat transfer fluid mass flux across the heattransfer surfaces will result in inadequate heating and a loss ofbenefit from providing the internal heating within the reaction zone.The heat exchange reaction section may be divided into multiple heatexchange reactor sections. Nevertheless each heat exchange reactorsection still requires a high mass flux rate to provide adequate heatingacross all of the heat transfer surfaces.

Even with separate reaction zones or reaction stacks, as they arereferred to herein, the maximum temperature for the heat transfer fluidalso remains limited. Constraints on the temperature of the heattransfer fluid as providing heating to the reactants can typically applyto minimum or maximum values. Minimum allowable temperature must be highenough to induce a reaction rate that exceeds what would ordinarily beobtained from an adiabatic process. However, at the same time, themaximum temperature at which the heating fluid enters the heat transferzone must not heat the reactants to a temperature that can cause a lackof selectivity in the products produced, or worse, a decomposition ofthe products already produced.

For example, in the dehydrogenation of ethylbenzene, the processrequires that the endothermic heat of reaction be supplied internally orexternally. In an adiabatic reactor operation, the sensible heat in thefeed stream provides the endothermic heat of reaction. Mixing a largequantity of super heated steam to the ethylbenzene feed increases theavailable sensible heat. Limitations in the ability to provide heatingby sensible heat restricts the maximum allowable temperature drop acrossthe reactor. However, using excessive steam temperatures to maintain aminimum reaction temperature will exceed the maximum sensitivitytemperature for the ethylbenzene and begin its decomposition.Furthermore, designing equipment for the more severe operatingconditions significantly increases its cost. Again, the endothermic heatof reaction may also be supplied by indirect heat exchange from anappropriate heat transfer fluid. Nevertheless, providing sufficient massflux to all of the heat transfer surfaces will require a high heattransfer fluid mass flow rate which would lead to larger equipment sizesand higher processing costs.

Accordingly, it is an object of this invention to reduce the heattransfer fluid mass flow rate required to provide the necessary heattransfer fluid mass flux to maintain a high reaction temperature withoutexceeding the sensitivity temperature of the reactants or the productsproduced by their reaction.

It is a further object of this invention to provide a reactor apparatusfor the indirect heating of a reactant stream in a reaction zone whileconserving heat and reducing the necessary mass flow rate to provide agiven mass flux over the heat transfer surfaces.

BRIEF SUMMARY OF THE INVENTION

This invention uses a multiple-pass heat exchange configuration to heatreactants indirectly with a heat exchange fluid in groups of stackedplates that provide reaction zones having reaction channels and heatexchange channels. The multiple pass arrangement of this inventionsignificantly improves heat transfer. In turn the multiple-pass heatexchanger effectively reduces the heat transfer fluid mass flow rate forendothermic reacting systems while maintaining the equivalent overallheat flux across the heat transfer surfaces that separate the reactionchannels from the heating channels. This arrangement reduces the size ofthe heat transfer equipment. The invention may also be used to increasethe heat flux while maintaining a constant heat transfer fluid mass flowrate. The invention uses a series flow of the heat transfer fluidthrough reactors that receive a parallel flow of reactants. Thiscombination of flows permits the control of the process site temperatureprofiled in the reactant channels to a variety of desired shapes. Theprocess also enhances the isothermal operation of a reaction zone bymore uniformly distributing heat along the catalyst beds. Thearrangement improves process and heat transfer flow distributions forco-current, counter-current, or cross-current operations. Serial flowmaintains the heat transfer fluid mass flow rates across the heatingchannels for multiple reaction stacks and reduces capital and operatingcosts thereby lowering equipment sizes and utility requirements. Theflexibility for controlling the temperature of the heat transfer fluidfacilitates the use of a variety of heat transfer fluids such as steam,flue gas, liquid sodium, molten salt, and in-situ combustion to be usedmore efficiently.

This invention can be particularly useful with the use of high heatcapacity heating fluids such as molten salts and liquid metals. Inparticular, liquid sodium has a heat capacity and thermal conductivitythat are, on a volumetric basis, superior to most heat transfer mediums.Liquid sodium is known to work for use in dehydrogenation processesincluding paraffins and aromatics. Despite its excellent heat transferproperties even an excellent heating medium such as liquid sodium mayrequire a mass ratio of heating fluid to process feed as high as 30 toobtain isothermal profiles. The heat transfer piping circulates liquidsodium or other heating fluid the multiple reaction stacks in seriesflow while the process piping passes the feed through the reactionstacks in parallel. In this manner, for each reaction stack orindividual heat transfer reactor provided: in parallel, the mass flowrate of the process feed is reduced inversely to the total number ofparallel reaction zones while the total of the heating fluid mass fluxto heat transfer surfaces is maintained through the reheating of theheating fluid between the series of reactors. The heating fluid of thisinvention is not limited to liquid metal or molten salts and may includelower heat capacity fluids such as, hot oil, steam, or flue gas. Thereheating of flue gas may be improved by the addition of small amountsof methane or other flue for direct combustion in the heat transfermedium.

The invention may be particularly useful for providing a heating fluidby catalytic combustion of a fuel stream. The rate of combustion of thefuel mixture could be controlled thereby distributing the heat releaseacross more of the heat transfer surface to improve the process reactionprofile in terms of selectivity and activity in the reaction channels.

This invention has been found to be particularly effective in thedehydrogenation of ethylbenzene to produce styrene. By improving theuniformity of the heat transfer rate across a heat transfer surface,this invention increases the selectivity for styrene production by up to1.2% over traditional ethylbenzene dehydrogenation processes. Wheresteam was used as the heating fluid, the invention improved the usualproduction over that achieved by adiabatic reactors through the use ofmultiple-stage heating fluid flow through a plurality of parallelethylbenzene dehydrogenation reactors. In particular, this inventionimproves the use of steam as a heating medium in the ethylbenzenedehydrogenation process. Processes for the production of styrenetypically require a large amount of steam. This invention uses the steamfirst as the heating fluid and then injects the steam after heattransfer into the process feed to satisfy the required steam-to-oilratio. Low steam-to-oil ratios are preferred to reduce utilities andoperating costs. This invention facilitates the use of low steam massflow rates while still providing the necessary heating into the reactionchannels. Metallurgical limitations of the reactor will generallyrestrict steam temperatures to below 800° C. and, more practically, tobelow 650° C. This invention increases the heat flux for the steam bypiping the steam in series to the heating channels of the reactionstacks and by reheating the steam up to 16 times.

Accordingly, in one embodiment, this invention is a process forcontacting reactants with a particulate catalyst in a channel reactorwhile indirectly contacting the reactants with a heating fluid. Theprocess retains catalyst particles in a plurality of reaction stacks.Each reaction stack contains a plurality of vertically and horizontallyextended reaction channels in a plurality of vertically and horizontallyextended heating channels for providing indirect heat exchange. Areactant stream passes to at least two of the reaction stacks inparallel flow and contacts the catalyst therein. A heating fluid passesthrough the heat exchange channels of at least two reaction stacks tocreate series flow of heating fluid through the reaction stacks. Theheating fluid undergoes reheating as it passes from one reaction stackto another reaction stack. The heating fluid is recovered from the lastreaction stack in the series of reaction stacks. At least a portion ofthe heating fluid returns to the first reaction stack in the series. Theprocess recovers a reactant stream from the plurality of reactionstacks.

In another embodiment, this invention is a channel reactor apparatus forcontacting reactants with a particulate catalyst, indirectly heating thereactants with a heating fluid and reheating the heating fluid with aheat source in a heater. The apparatus contains a plurality of reactionstacks with each reaction stack comprising a plurality of parallelplates extending vertically and horizontally. The reaction stacks defineheating channels and reaction channels. A distribution system passes areactant stream to the reaction channels of each reaction stack inparallel flow. A withdrawal system collects the parallel flows ofreacted reactants from each reaction stack. The heating fluid deliveryconduit delivers a heating fluid to the heating channels of one of thereaction stacks located in a lead position. A plurality of intermediateconduits pass the heating fluid in series flow from the reaction stackin the lead position through the heating channels of reaction stackslocated in the intermediate position and finally to a reaction stacklocated in an end position. A heating fluid recovery conduit recoversthe heating fluid from the reaction stack in the end position. A heaterreheats the heating fluid that passes through each intermediate conduit.

Additional embodiments, arrangements, and details of this invention aredisclosed in the following detailed description of the invention.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a sectional elevation of a reactor arranged in accordance withthis invention.

FIG. 2 is a section taken along line 2—2 of FIG. 1

FIG. 3 is a schematic representation of a reaction stack and the flow ofcatalyst, reactants, and heat exchange medium therethrough.

FIG. 4 is cross-section of the reaction stack taken along line 4—4 ofFIG. 3.

FIG. 5 is sectional elevation of a reactor arranged in accordance withthis invention and modified from FIG. 1.

FIG. 6 shows a horizontal cross-section of a reactor containing reactionstacks similar to those shown in FIGS. 1-4, in an alternate arrangement.

FIGS. 7 and 8 are graphs showing the performance of a traditionalstyrene production system.

FIGS. 9 and 10 are graphs showing the performance of the reactorarrangement of this invention for the production of styrene.

DETAILED DESCRIPTION OF THE INVENTION

The process may be useful in a wide variety of catalytic reactions.Suitable processes may use heterogeneous or homogeneous catalysts.Suitable reaction zone arrangements may also employ catalyst beds thatare fixed, moving, or fluidized beds. This invention is mostbeneficially applied to catalytic conversion processes having highendothermic heats of reaction. Reactions of this type include thereforming of hydrocarbons and the dehydrogenation of hydrocarbons. Thisinvention may be applied to processes having high exothermic heats ofreaction such as hydrocarbon oxidation, ammonia synthesis, phthalicanhydride production, and ethylene oxide formation.

Most catalysts for the reaction of hydrocarbons are susceptible todeactivation over time. Deactivation will typically occur because of anaccumulation of deposits that cause deactivation by blocking active poresites or catalytic sites on the catalyst surface. Where the accumulationof coke deposits causes the deactivation, reconditioning the catalyst toremove coke deposits restores the activity of the catalyst. Coke isnormally removed from the catalyst by contact of the coke-containingcatalyst at high temperature with an oxygen-containing gas to combust orremove the coke in a regeneration process. The regeneration process canbe carried out in situ or the catalyst may be removed from a vessel inwhich the hydrocarbon conversion takes place and transported to aseparate regeneration zone for coke removal. Arrangements forcontinuously or semi-continuously removing catalyst particles from a bedin a reaction zone for coke removal in a regeneration zone are wellknown. U.S. Pat. No. 3,652,231 describes a continuous catalystregeneration process which is used in conjunction with catalyticreforming of hydrocarbons, the teachings of which are herebyincorporated by reference. In the case of the reaction zone, thecatalyst is transferred under gravity flow by removing catalyst from thebottom of the reaction zone and adding catalyst to the top. U.S. Pat.No. 5,073,352 and U.S. application Ser. No. 09/058,606 filed Apr. 10,1998, now abandoned, describes a method and apparatus for movingcatalyst through channel reactors.

The reaction zones for the process of this invention may indirectlycontact the reactants with the heat exchange fluid in any relativedirection. Thus, the flow channels, inlets, and outlets of the reactionzones may be designed for co-current, counter-current, or cross-flow ofreactant relative to the heat exchange fluid. Cross-flow of reactants isused reduce the flow path length through the reactor thereby minimizingthe pressure drop associated with the flow of reactants through thereactor and simplifying mechanical design. For this reason, a cross-flowarrangement can be used to provide the reactants with a shorter flowpath across the reaction zone.

Preferred process arrangements for practicing this invention will passreactants in co-current-flow with respect to the heat exchange fluid.Co-current flow offers the best compatibility with most processkinetics. More heat is usually released or absorbed by the processreaction near the inlet of the reaction zone. Co-current flow favorshigh heat transfer near the inlet of the reaction of the reaction zone.

The shorter flow path reduces overall pressure drop of the reactants asthey pass through catalyst particles retained in the reactor. Lowerpressure drops can have a two-fold advantage in the processing of manyreactant streams. Increased flow resistance i.e., pressure drop, canraise the overall operating pressure of a process. In many cases,product yield or selectivity is favored by lower operating pressure sothat minimizing pressure drop will also provide a greater yield ofdesired products. In addition, higher pressure drop raises the overallutility and cost of operating a process.

It is also not necessary to the practice of this invention that eachreactant channel be alternated with a heat exchange channel. Possibleconfigurations of the reaction section may place two or more heatexchange channels between each reactant channel to reduce the pressuredrop associated with the circulation of the heating medium. When usedfor this purpose, a plate separating adjacent heat exchange channels maycontain perforations.

The type and details of the reactor arrangement contemplated in thepractice of this invention are best appreciated by reference to thedrawings. FIG. 1 is a schematic representation of a catalytic reactorsection designed to effect a catalytic reaction on a reactant fluidwhile using indirect heat exchange with a heat transfer fluid tomaintain favorable reaction temperatures as the reactant fluid flowsthrough the reaction section. The reactor contains multiple reactionstacks. The reactor section contains means for sequentially reheatingthe heating fluids as it flows out of the reactor sections of eachreaction stack. The reactor effects catalytic reaction of a flowingreactant fluid under controlled temperature conditions by indirectcontact with a flowing heat transfer fluid. Movement of catalyst throughthe reaction stacks is possible, but usually requires the reduction orstoppage of the reactant flow before the particulate catalyst can move.

The reactor section comprises a reactor vessel 12 having a circularcross-section. The reactor vessel 12 has an elliptical head 14. Anotherelliptical head 18 closes the bottom of reactor vessel 12 and supports aplenum 10 of a withdrawal system. Reactants and steam flow throughinlets 11 and 13 into a manifold 20 that provides part of a distributionsystem 15 for disiributing the reactants into reactant inlet pipes 24.As shown in FIG. 2, reactant inlet pipes 24 feed the reactant streaminto a distribution space 26. Reactants flow horizontally acrossreaction stacks 28 through vertically extended reactant flow channelsdefined therein. A collection space 30 collects reaction products fromthe reactant channels. Collector pipes 32 withdraws the reactionproducts from each collection space 30 into a withdrawal system 16 (seeFIG. 1) that transports the reaction products out of the reactor vesselvia a line 34. In the arrangement of FIGS. 1 and 2, each reactant inletpipe 24 supplies reactants to two reactant stacks 28 while each outletpipe 32 withdraws reactant products from two reaction stacks 28. Theoffsetting of the reactant inlet pipes 24 to the outlet pipes 32 resultsin each outlet pipe 32 withdrawing reactants supplied by two differentreactant inlet pipes 24.

Looking again at FIG. 1, the reactor 12 also contains heaters 17 and 17′for reheating the heating fluid as it passes from one reaction stack (28or 28′) to the next. Looking again at FIG. 1, cold heating fluid entersreactor 12 through a line 19 and passes through a first heater 17. Aline 21 passes the heated fluid to a series of delivery conduits 23 thatdeliver the heating fluid to the reaction stacks 28 via heat transfermanifolds 25. Heat transfer manifolds deliver the heating fluid to theheating channels in reaction stacks 28. Another series of collectionmanifolds (not shown) withdraw the cooled heating fluid from thereaction stack 28 and deliver it to an intermediate conduit systemcomprising an inlet conduit 27 and an outlet conduit 29. Intermediateconduits 27 and 29 reheat the heating fluid in another heater 17′.Heated fluid from heater 17′ passes into reaction stack 28′ via anotherseries of delivery conduits and distribution manifolds (not shown). Aplurality of collection manifolds 31 spaced down reaction stack 28′recover the heating fluid through a plurality of recovery conduits 33that deliver the heating fluid to a central recovery conduit 35.Recovery conduit 35 will typically return at least a portion of theheating fluid back to inlet conduit 19. Recovery conduit 35 recovers theheating fluid from the reaction stack 28′ that is in an end position.Inlet conduit 21 delivers the heat exchange fluid to a reaction stackthat is in a lead position. If any intermediate reaction stacks areprovided, similar piping would move the heating fluid out of onereaction stack to an intermediate feeder and into another reactionstack.

FIG. 2 shows that an additional layout arrangement for supplying a superheating fluid to the different heaters 17 and the interconnecting pipingbetween the reaction stacks 28. The external heating fluid may besupplied to the heaters 17 via a line 41.

The intermediate heating provided between the reaction stacks may beprovided externally to the reaction zone, but is preferably provided asshown in FIGS. 1 and 2 by internal heaters. The internal heaters may bein the form of indirect heat exchangers, fired heaters or simply asystem for introducing fuel into the heat exchange media for in-situcombustion which again reheats the heat exchange fluid. For example, theheater may comprise an injector that injects a combustion reactant intothe intermediate conduit. Containing the heaters within the reactorprovides an overall benefit of maintaining heating efficiency byperforming the heat exchange within the reaction vessel to minimize oreliminate heat loss to the atmosphere associated with the reheating ofthe fluid passing through reaction stacks.

Where heaters 17 provide indirect heat exchange, a heating fluid 37enters the heater 17 and exits after indirect heat exchange via aconduit 39′. The heater 17 may be any form of indirect heat exchange orthat will provide an efficient heat exchange between the external heatexchange fluid and the internal heating fluid that passes through thereaction stacks. A distribution header 43 delivers the fluid forreheating the heating fluid to the individual heaters 17. Anothercollection header 45 recovers the cooled reheating fluid from the heater17 and withdraws it from the reaction vessel 12 through a line 47. FIG.2 also shows the heating fluid entering the reaction vessel 12 through aline 49 into the reaction stack 28 in the lead position and thewithdrawal of heating fluid via a line 51 from the reaction stack in theend position.

The reactant stream typically contacts a particulate catalyst in each ofthe reaction stacks. The catalyst will usually be present as discreteparticles usually in a size range of from 1 to 15 mm in diameter. Theparticles may have any shape, but they will typically comprise spheresor cylinders. Catalyst for passage into the reactant channels enters thereaction stacks 28. Catalyst enters the top of the reactor vessel 12through catalyst loading conduits 38 after passage through the reactionchannels in reaction stacks 28, catalyst flows out of the reactionstacks 28 and reaction vessel 12 through catalyst transfer pipes 50.

The arrangement and operation of the reaction stacks is shown moreclearly by a schematic representation in FIGS. 3 and 4. Each reactionstack 28 comprises a plurality of parallel plates 72 as shown in FIG. 4.Suitable plates for this invention will comprise any plates that allow ahigh heat transfer rate. Thin plates are preferred and usually have athickness of from 1 to 2 mm. The plates are typically composed offerrous or non-ferrous alloys such as stainless steel. Each plate 72 maybe smooth, but preferably has corrugations that are straight or inclinedto the flow of reactants and heat exchange fluid. The plates may beformed into curves or other configurations, but flat plates aregenerally preferred for stacking purposes. The corrugated plates may bestacked directly next to each other with the space between corrugationsdefining alternate reactant channels 73 and heat exchange channels 74.Where plates 72 contain inclined corrugations, the plates may be stackednext to each other to define the heat exchange and reactant flowchannels as the area between corrugations. Preferably the corrugationpattern will be reversed between adjacent plates so that a herring bonepattern on the faces of opposing corrugated plates will extend inopposite directions and the opposing plates faces may be placed incontact with each other to form the flow channels and provide structuralsupport to the plate sections.

FIG. 3 shows a modified arrangement of delivery and collection manifoldsfor the reaction stacks 28. This modified arrangement moves the heatingfluid in a vertical down flow direction as opposed to the horizontalflow shown in FIGS. 1 and 2.

The heating fluid enters the process through an inlet header (not shown)that distributes the heating fluid to distribution pipes 66.Distribution pipes 66 supply heat exchange fluid to a heat exchangemanifold 64 at the bottom of each reaction stack 28 The heat exchangefluid flows vertically down the heat exchange channels in each reactionstack into a collector manifold 62 at the bottom of each heat exchangestack 28. Collection pipes 60 feed the heat exchange fluid into acollection manifold (not shown) which withdraws heat exchange fluid.

Each reaction stack includes in its upper part an inlet for receivingthe heat exchange fluid into circulation system “B”. The inlet may be asingle opening. FIGS. 3 and 4 show the manifolds 64 and 62 fordistributing and collecting heat exchange fluid from the top and thebottom, respectively of reaction stack 28. Manifolds 64 and 62communicate with the heat exchange channels 74 through openings in thesides 77 that are located at the top and bottom on opposite sides of thereaction stack. The manifolds provide a distribution area on the sidesof the reaction stack. In the distribution area covered by manifolds 64and 62, the sides 76 of the reactant channels are closed to prevent theentry of the heat exchange fluid into the reactant channels.

Catalyst particles 75 normally fill the reactant flow channels 73. Thesides 76 of reactant flow channel 73 are closed to catalyst flow by apermeable closure 76 that still permits the flow of reactants in thedirection indicated by arrows “A”. The sides 77 of heat exchangechannels 74 have a fluid impermeable closure that holds the heatexchange fluid over the length of channel 74. The tops of the heatexchange channels are closed to prevent catalyst entry therein. As shownin the reaction stack of FIG. 3, the heat exchange fluid flowsdownwardly as indicated by arrows “B” such that the reaction stackdefines a specific circulation system for flows “A” and “B” wherein thereactant stream “A” and the heat exchange fluid “B” flow in crosswisedirections and through alternate channels formed by adjacent plates 72.

Catalyst particles 75 flow into the top of reactant channel 73 throughdiffuser 52. Diffuser 52 may contain internal baffles or corrugations 78for distributing catalyst evenly across the top of the reactantchannels. Similarly, collector 54 at the bottom of reactant channel 73collects the catalyst particle 75 and may contain baffles orcorrugations 80. The baffles or corrugations in the diffuser andcollector promote a uniform replacement of catalyst across the entirehorizontal length of each reactant channel 73.

The reactor arrangement may be modified to place the heaters indifferent locations. FIG. 5 shows an arrangement of a reaction vessel 51having a plurality of reaction stacks 53. The arrangement locatesheaters 55 above the reaction stacks and heaters 57 below the reactionstacks. In a manner similar to that previously described in conjunctionwith FIGS. 1 and 2, mixed feed enters the bottom of the reactor systemthrough a distribution system 59 that receives reactant and steam fromlines 11′ and 13′ respectively. A withdrawal system 61 collects reactedreactants from the top of the reaction stack for withdrawal from thereactor 51. Catalyst may again be added and withdrawn from the reactorvessel 51 through upper conduit 63 and lower conduit 65. Heaters 55 and57 receive a super heating stream from line 67 that is distributed tothe heaters. A conduit 69 collects the cooled stream of heat exchangefluid after it passes through heaters 55 and 57. Heaters 57 provideindirect heat exchange with the reheating fluid supplied by conduits 67.

The heating fluid may be circulated between heaters 55 and 57 andreaction stacks 53 in any desired manner. In the arrangement of FIG. 5heated heating fluid flows out of heater 55′ through a conduit 80 anddownwardly through reaction stack 53′. A lower conduit 81 recovers thecooled heating fluid and passes it to the bottom of heater 57′. Heater57′ reheats the heating fluid by heat exchange with the reheat fluidfrom line 67. The hot heating fluid flows into the bottom of reactionstack 53″ via a line 82. The heating fluid flows upwardly throughchannels in reaction stack 53″. An intermediate conduit 83 transferscooled heating fluid from the top of reaction stack 53″ to the top ofheater 55. Reheat fluid 67 again heats the heating fluid as it passesdownwardly through heater 55. Reheat fluid passes from heater 55 toreaction stack 53 through a conduit 84. The circulation of heating fluidcontinues in a similar manner as it leaves the bottom of reaction stack53 through a conduit 85 and passes into the bottom of heater 57. In thismanner, the circulation of the heating fluid changes direction througheach reaction stack 53 while passing downwardly through each heater 55and 57.

In addition to the heat exchange circulation, the process may beoperated in a variety of other ways. Flow into the reaction stacks orout of the reaction stacks may be arranged to control multiple reactionstacks at one time as shown by the embodiment of the invention in FIGS.1-5. The arrangement of the reaction stacks may also be modified to havecentral collection or distribution of reactants with withdrawal from theperiphery. Alternately, the flow of reactants into or products out ofeach reaction stack may be individually controlled. An arrangement forthe radial flow of reactants into or out of each reaction stack is shownin FIG. 6. FIG. 6 shows a horizontal cross-section of a reactorcontaining reaction stacks similar to those shown in FIGS. 1-5. FIG. 6differs from FIGS. 1-5 in that the reaction stacks 110 are arrangedcircumferentially in a polygonal arrangement around a central space 112that can serve as a distributor or as a collector. A baffle 116surrounds the outside 114 of each reaction stack 110. Baffle 116 againdefines a space at the outside of each reaction stack 110 that can serveas a collector or distributor. Individual pipe openings 118 communicatewith the outer space 117 enclosed by each baffle 116. Appropriatevalving on the piping to outlet 118 can selectively restrict or stopflow through each individual reaction stack. All of the reaction stacksmay again be surrounded by a reaction vessel 120 to provide pressurecontainment for the reaction.

The arrangement of this invention can be particularly suited for thedehydrogenation of paraffinic feedstocks. The dehydrogenation ofethylbenzene to produce styrene is well known. Paraffinic feedstocksordinarily have from about 3 to about 18 carbon atoms. Particularfeedstocks will usually contain light or heavy paraffins. A catalyticdehydrogenation reaction is normally effected in the presence ofcatalyst particles comprised of one or more Group VII noble metals(e.g., platinum, iridium, rhodium, and palladium) combined with a porouscarrier such as a refractory inorganic oxide. Alumina is a commonly usedcarrier. Dehydrogenation conditions include a temperature of from about400° to about 900° C., a pressure of from about 0.01 to 10 atmospheres,and a liquid hourly space velocity (LHSV) of from about 0.1 to 100 hr⁻¹.Generally, the lower the molecular weight of the feed the higher thetemperature required for comparable conversions. The pressure in thedehydrogenation zone is maintained as low as practicable, consistentwith equipment limitations, to maximize the chemical equilibriumadvantages. The preferred dehydrogenation conditions of the process ofthis invention include a temperature of from about 400° to 700° C. and apressure from about 0.1 to 5 atmospheres. Additional information on thedehydrogenation of paraffins can be found in U.S. Pat. Nos. 4,677,237,4,880,764, and 5,087,792.

This invention is particularly adapted for the production of styrene bythe dehydrogenation of ethylbenzene using a heating fluid to maintainthe temperature of the reaction zone at favorable condition forselectivity and conversion. In a typical arrangement such as that shownin FIGS. 1-5, the total ethylbenzene feed enters in parallel to each ofeach reaction stacks containing catalyst. The feed has a fixedsteam-to-ethylbenzene ratio. The heating fluid enters in co-current flowwith respect to the feed throughout the reactor length and passes alongthe surface of each bundle in series inside the reaction stacks. Theheat transfer fluid upon leaving a single reaction stack is reheated tothe appropriate temperature before entering the next reaction stack. Thereaction stacks can use a variety of different heat transfer fluids suchas liquid sodium, flue gas, steam, or even selective oxidation of thehydrogen that is produced through the dehydrogenation process. Thecombustion of the hydrogen from the dehydrogenation may take place inthe heaters and provide the heating fluid for indirectly reheating theheating fluid that circulates through the reaction stacks and theheaters.

More specifically, in such an arrangement, an ethylbenzene feed wouldenter parallel channel paths of the reaction stacks. As feed passedalong the reaction stack, flow paths would contact the dehydrogenationcatalyst. Heat from the heating fluid would pass across the heattransfer plates from the heating channel to the reaction channel. Amixture of ethylbenzene, styrene, and hydrogen generated from thedehydrogenation reaction would exit the reactor.

Conditions for the dehydrogenation of ethylbenzene to produce styrene iswell known. A catalytic dehydrogenation reaction is normally effected inthe presence of an iron oxide catalyst. Suitable catalysts comprising atleast 35 wt-% iron oxide are described in U.S. Pat. Nos. 3,387,053.4,467,046 describes a benzene dehydrogenation catalyst that contains 15to 30 wt-% potassium oxide, 2 to 8 wt-% cerium oxide, 1.5 to 6 wt-%molybdenum oxide, 1 to 4 wt-% calcium carbonate, with the balancecomprising iron oxide. Ethylbenzene dehydrogenation conditions include atemperature of from about 400° to about 900° C., a pressure of fromabout 0.01 to 10 atmospheres, and an LHSV of from about 0.1 to 2 hr⁻¹.The pressure in the dehydrogenation zone is maintained as low aspracticable, sometimes under vacuum, consistent with equipmentlimitations, to maximize the chemical equilibrium advantages. Thepreferred dehydrogenation conditions of the process of this inventioninclude a temperature of from about 400° to 700° C. and a pressure fromabout 0.1 to 5 atmospheres.

In a preferred form of a styrene production process, a super-heatedsteam stream would enter the heaters via a distribution header and thesuper-heated steam will usually be added in a quantity that will producea steam-to-ethylbenzene ratio of approximately 0.5 to 2, and morepreferably 0.7 to 1.5 at the inlets to reaction channels. Passage of thestream through the channels of the heater efficiently heats the heatingfluid by virtue of the large surface area provided by heat transferplates. Manifold space redistributes the stream after it passes throughthe heaters and mixes it with the entering ethylbenzene feed to promotethe dehydrogenation reaction of the steam and ethylbenzene mixture as itpasses into the reaction channels. Some form of pipe distributor may beuseful to distribute the ethylbenzene feed. The reaction channelscontain an ethylbenzene dehydrogenation catalyst. Catalyst material mayreside in the channels as a coating applied to the plates or as discreteparticles retained in the channels by an appropriate. screen materialacross inlets. Indirect heating across plates by the heating fluidcompensates for the cooling effect of the endothermic dehydrogenationreaction as the ethylbenzene and steam mixture passes up reactionchannels.

A collection space collects the dehydrogenation zone product stream fromthe reaction channels. The collected reactor effluent mixture ofstyrene, ethylbenzene, and steam is transferred into a product line forrecovery of product components and recycle of reactants and steam. Theeffluent stream from the dehydrogenation zone generally will containunconverted hydrocarbons, hydrogen, and the products of dehydrogenationreactions. This effluent stream is typically cooled and passed to ahydrogen separation zone that separates a hydrogen-rich vapor phase froma hydrocarbon-rich liquid phase. Generally, the hydrocarbon-rich liquidphase is further separated by means of a suitable selective solvent, aselective reaction or reactions, or by means of a suitable fractionationscheme. Unconverted dehydrogenatable hydrocarbons are recovered and maybe recycled to the dehydrogenation zone. Products of the dehydrogenationreactions are recovered as final products or as intermediate products inthe preparation of other compounds. Additional information related tothe operation of dehydrogenation catalysts, operating conditions, andprocess arrangements can be found U.S. Pat. No. 5,043,500, the contentsof which are hereby incorporated by reference.

Passing the super-heated stream through the heaters raises thetemperature of the circulating heating fluid between each reactionstack. In this manner, the super-heated steam may have temperatureshigher than the sensitivity temperature that would cause decompositionof the styrene products and may also require special metallurgy thatwill allow higher operating temperature, but the need for expensivemetallurgy is limited to only the heaters for reheating, which greatlyreduces the overall cost of providing the reaction stacks for the heatexchange type reaction arrangement. Preferably, the heating fluid is ahigh capacity heat transfer fluid that moderates the temperature of thesteam as it cools in the heaters so that the dehydrogenation reactionoccurs at an essentially uniform temperature in the reaction stacks.

EXAMPLES

These examples compare the overall start of run yield estimates betweena traditional two-reactor styrene process and a styrene process inaccordance with this invention that uses eight parallel pass reactionstacks. These examples are generated from computer simulations of modelsfor the specific operation of a styrene process using known kineticparameters of the dehydrogenation reactions along with experimentallyverified heat transfer coefficients across the common boundary of thereaction in heating channels to provide the results. The kineticinformation is based on activities for that of a commercial iron oxidetype dehydrogenation catalyst.

Example I

This example operates two reactors in series in an adiabatic manner. Theprocess temperature and pressure at the inlet and outlet of eachreactor, as well as the composition of the feed stream entering andexiting the two reactors is shown in Table 1. The process passes eachreactant stream through the reactors at an LHSV of 1 and a catalystvolume in each reactor of about 92 cubic meters. The catalyst was ⅛-inchsize extrudite that was loaded to avoid fraction of about 0.45. Theparticles had a Reynolds Number of 48. The feed entered at asteam-to-oil ratio of 1.35. Ethylbenzene conversion in the first reactorwas 40.4%, and in the second reactor 68%. The styrene selectivity fromthe second reactor was 97.84 mol-%. FIGS. 7 and 8 show the conversionand selectivity performance for the overall process.

Example II

This example passes the feed stream having the composition given inTable 2 as eight separate streams to eight parallel reaction stacks. Thereaction stacks provide a reactant path length 1.05 meters and a heatingfluid path length of the 13 meters. The arrangement uses a total of 672process channels and 680 heating channels. The catalyst has essentiallythe same properties as those used in Example I. The steam-to-oil ratiofor the feed is 1. Table 2 also shows the inlet and outlet temperaturesfor each of the reaction stack which operated at essentially the sameconditions. The process circulated the heat transfer fluid through eachof the reaction stacks that entered at a temperature of 640° C. and lefteach reaction stack at a temperature of 590° C. Intermediate heating ofthe heating fluid as it passed in series flow through the reactionstacks provided recovery of the inlet temperature to 640° C. The heattransfer media had a total flow rate of 79,400 kg/hr. Results forselectivity and conversion using the intermediate reheat arrangement ofExample 3 is shown in FIGS. 9 and 10.

Example II was simulated for both a steam heating fluid and a liquidsodium heating fluid. When using the steam heating fluid, a selectivityincrease of 0.8 mol-% was observed. When using the liquid sodium as theheat transfer fluid, a maximum 1.2 mol-% increase in the selectivity wasobserved. The catalyst bed size could also be reduced by 50% whencompared to a traditional styrene process.

TABLE 1 Reactor Reactor Reactor Reactor No. 1 No. 1 No. 2 No. 2 InletOutlet Inlet Outlet Process Temperature, ° C. 610 529 619.3 564 ProcessPressure, psig −5.9 −7.03 −7.497 −8.6 Components, kg/hr Ethylbenzene78130 46555 46555 24994 Styrene 635 30857 30857 51227 Benzene 64 269 269461 Toluene 564 983 982 1443 Hydrogen 0 608 608 1036 Methane 0 50 50 91Ethylene 0 27 27 38 Carbon Dioxide 0 204 204 484 Carbon Monoxide 0 6 613 Steam 107619 107004 107004 106774 Total 186562 186562 186562 186562

TABLE 2 Inlet Outlet Process Temperature, ° C. 567 587 Process Pressure,psig 7.3 8.7 HTM Duty, MBU/hr 66.86 Components, kg/hr Ethylbenzene 7811424980 Styrene 644 51645 Benzene 81 444 Toluene 564 1137 Hydrogen 0 1026Methane 0 67 Ethylene 0 47 Carbon Dioxide 0 328 Carbon Monoxide 0 14Steam 79397 79112 Total 158800 148800

What is claimed is:
 1. A channel reactor apparatus for contactingreactants with a particulate catalyst, indirectly heating the reactantswith a heating fluid and reheating the heating fluid with a reheatingfluid, said apparatus comprising: a plurality of reaction stacks witheach reaction stack comprising a plurality of parallel plates extendingvertically and horizontally and defining heating channels and reactionchannels in each reaction stack; a distribution system for passing areactant stream to the reaction channels of each reaction stack inparallel flow; a withdrawal system for collecting the parallel flow ofreacted reactants from each reaction stack; a heating fluid deliveryconduit for delivering a heating fluid to the heating channels of one ofthe reaction stacks located in a lead position; a plurality ofintermediate conduits for passing the heating fluid in series flow fromthe reaction stack in the lead position, through the heating channels ofreaction stacks located in an intermediate position, and to a reactionstack located in an end position; a heating fluid recovery conduit forrecovering the heating fluid from the reaction stack in the endposition; and a heater for reheating the heating fluid as it passesthrough an intermediate conduit.
 2. The apparatus of claim 1 wherein theapparatus includes means for adding catalyst particles to the top andwithdrawing catalyst from the bottom of each reaction stack.
 3. Theapparatus of claim 1 wherein the heater comprises an exchanger forindirect heat exchange between the heating fluid and a superheatingfluid.
 4. The apparatus of claim 1 wherein the heater comprises aninjector that injects a combustion reactant into the intermediateconduit.
 5. The apparatus of claim 1 wherein a reaction vessel surroundsthe reaction stacks and contains the heater.
 6. The apparatus of claim 5wherein at least a portion of the heaters is located above or below thereaction stacks.
 7. The apparatus of claim 1 wherein the reaction stackscomprise a plurality of corrugated plates that define the heatingchannels and the reactant channels.
 8. A channel reactor apparatus forcontacting reactants with a particulate catalyst, indirectly heating thereactants with a heating fluid and reheating the heating fluid with areheating fluid, said apparatus comprising: a plurality of reactionstacks with each reaction stack comprising a plurality of parallelplates extending vertically and horizontally and defining heatingchannels and reaction channels in each reaction stack; a distributionsystem for passing a reactant stream to the reaction channels of eachreaction stack in parallel flow; a withdrawal system for collecting theparallel flow of reacted reactants from each reaction stack; a heatingfluid delivery conduit for delivering a heating fluid to the heatingchannels of one of the reaction stacks; a plurality of intermediateconduits for passing the heating fluid in series flow from the heatingchannels in one of the reaction stacks through the heating channels ofanother of the reaction stacks; a heating fluid recovery conduit forrecovering the heating fluid from one of the reaction stacks; and aheater for reheating the heating fluid as it passes through at least oneof the intermediate conduits.